Modification of fatty oils



Patented Aug. 27, 1946 UNITED STATES A PATENT OFFICE MODIFICATION OF FATTY oILs V Laszlo Auer, South Orange, N; J.

No Drawing. Application januaryaz3, 1943, V Serial N0.47 3,396 f I 22 Claims. (01. 260-407) GENERAL FIELD or INVENTION ANDMSTATEL MENT OF OBJECTS hydroxy benzenes, such as dihydroxy and trihydroxy benzenes, the mixture being heated to elevated temperatures. I have secured particularly good results with resorcinol, which isadihydroxy benzene. Full description ofthe treatment procedure is given hereinafter. I I

' According to the present invention, it is possible to achieve a number of advantages in the treatment of fatty oils. For example, it is possible to materially improve the drying characteristics of the fatty oil, and also to improve water and alkali resistance of film coatings or the like formed with the treated oil.

The foregoing and other objects and advantages Will appear more fully hereinafter, especially from consideration of examples given. Be-

fore proceeding with description of the treatment procedure, reference is now made to the-fatty oil materials to which the invention is applicable.

The process may be employed on fatty oils generally, including drying oils, semi-drying oils, and non-drying oils. The following is a typical list of such oils:

Tung oil Oiticica oil Dehydrated castor oil Linseed oil Perilla oil Poppyseed oil Soya bean oil Walnut oil Rapeseed oil Pine seed oil Olive oil Corn oil Cottonseed oil Coconut oil Babassu oil Hydroxylated oils such as castor oil, etc. Fish oils (train 'oils) dryin'g'and semi-' dr'y -In addition, it should be noted that esters of fatty acids other than the natural glycerin esters (fatty oils) may be used, for example, synthetic glycerin esters of fatty acids, and fatty acid esters formed with other polyhydric alcohols, such as glycols, pentaerythritol, mannitol, sorbitol, etc.

For convenience, all such materials are herein referred to merely as fatty oils.

The process may be employed on fatty oils themselves or on various mixtures of materials containing fatty oils, for instance, on varnishes or varnish bases of oleo-resinous types, Whether used clear or pigmented. Reference herein to varnish base means all or part of the varnish solids or film forming ingredients. Fatty acids may be added to the'reaction mixture, if desired.

TREATMENT PROCEDURE AND CONDITIONS As above noted, the treatment process involves heating the fatty oil, or the material containing same, in the presence of a polyhydroxy benzene, especially dihydroxy and trihydroxy benzenes. Particularly good results have been secured by the use of resorcinol which is a dihydroxy benzene;

and with'pyrogallol, which is l, 2, 3trihydroxy benzene.

The quantity of treating agent employed may i be varied over a considerable range, depending upon the extent of'modification desired, the temperature, the particular fatty'oil being treated, etc. From'a small fractional percentage, for instance, from about 0.05% or 0.1% up to about 30%, may be used, although ordinarily from about 0.5%-to about 5 or 10%,for instance, 2% is quite effective. In connection with treatment temperature, it may be saidthat in general temperatures from about the lowest dissolution temperature of the modifying agent up to about 350 C. are usable, although the temperature should not be above the point at which the fatty oil appreciably decomposes. a r V Thetime of treatment willvary in accordance with other factors such astemperature. percentage of treating agent, etc. Ordinarily thev time should be at least 30 minutes and most usually several hours,,for instance, from about 1 hour to.

with a varnish base or other composite materialincorporating a fatty oil material, such composite material then being heated under conditions such as those discussed above.

Agitation may advantageously be used during any mixing procedure, in order to aid thorough dispersion of the treating agent.

The treatment may be carried out under varying atmospheric conditions, both with respect to pressure and also with respect to the gas in contact with the reaction mixture. Thus, under some circumstances, the fatty oil or the mixture containing the fatty oil may be heated under vacuum,

. relatively low temperature followed by additional and under other conditions, atmospheric pressure p 7 may be used, and also superatmospheric pressure. It is frequently of advantage to exclude the airfrom the reaction mixture and this-may be done during any stage of treatment, either by employ- I ing Vacuum or by blanketing the surface of the batch with some non-oxidizingbr inert'gas, for instance, CO2, S02, HzS, or nitrogen. Still further, exclusion of air may be obtained by carrying. out .thejreaction in a closed vessel (but not necessarily under a positive pressure), in which event vapors or the like released from the reaction' mass may serve to dispel or exclude the air.

I have found vacuum'treatment to. be particularly effective, for instance, from about 100- m-ms.

Hg to about 450 mms. Hg internal pressure, although higher or lower pressures are also useable. With regardto the foregoing atmospheric conconditionsin the reaction vessel, itmay be noted thatcertainof the gases mentioned may be employed for their supplemental effect on the reaction, in which event, if desired, the gases may be bubbled through the reaction mixture.

In general, it may bepointed out that increasing any one of the variables: temperature; time or percentage of modifying agent, usually increases the rate and/or extent of the reaction.

The modifying'agents herein claimed may be employed (either simultaneously or sequentially) in combination with others disclosed, for instance, invarious of my 'copending applications and issued patents, some of which are mentionedhereinafter; V In addition, supplemental treatments'may be applied to the oil, either during or following the 'fluorescein and also with a combination 0 phthalic anhydride and resorcinol;

-Where a fatty oil is being treated to prepare it for incorporation ina varnish base of the oleoresinous type, oneparticularly advantageous procedure is as follows: In this case the treating agent may initially be added to and dispersed in the fatty oil at relatively low temperature, for instance, from about 75;C. to about 200 CL; and

then when the oil is incorporated in the varnish or varnish base, additional heating maybe applied at higher temperatures; in order to. carry out the full degree of modification of the oil contemplated.

Even when treating a fatty oil alone, it may' be advantageous to divide the, treatment into twostages, the first of which is carried on at' a relatively low temperature, and the latter of which is carried on at a higher temperature.

heating at a higher temperature), loss of treating agent is prevented or at least reduced.

The term fpre-oondensation (initial or primary'condensation) as used herein, means treatmer t under conditions of the type just mentioned 1 at temperatures below the sublimation point and for a time suchthat upon subsequent heating of the treated oil to higher or heat bodying temperatures the resorcinol no longer tends to sublime to any great extent.

EXAMPLES Inv order'todemonstrate the process linseed oil and'resorcinolwere selected'as typical of the starting materials and treating agents, these two being usedin' mostJof the examples given below.

To determine the most advantageous treatment conditions, several comparative series of experiments were carried'out, all utilizing resorcinol andhnseed oil. An analysis of these experiments will aid in an understanding of the invention. First, note that resorcinol has a boiling point of 27.615 0;, and melts at 116 C. When molten, it dissolves quite easily in fatty oils and even at temperatures belowits melting point, it is'soluble inv many fattyoils.

In spite of the fact that the boiling point of resorcinol is comparatively high, it sublimes out of fatty oils at temperatures below its boiling point. Furthermore, its boiling point is below the usual and preferred temperature range for bodying fatty .oils or for cooking varnishes.

COMPARATIVE'EXAMPLES 1 T0 5 Because of the foregoing characteristics, it is 1 advantageous to adopt some means or procedure for reducing loss of the treating agent by sublimation" or boiling. With this in mind, a series of' experiments were carried out in one liter'aluminum beakers provided.v with covers, using resor-' Ex. No Temperature Viscosity fifig g g A Slight. A Considerable. 3+ Do.

B+ Do. S Do.

A (The same oil without A heating).

The foregoing series indicated that sublimation increased in general with increase in temperature.

Following the initial treatment of the several batches as mentioned above, varnishes were pre- The cold water test was carried outby immersing one half of each panel (carrying the varnish film) in cold water for 24 hours; and observing the milkiness of the film and the rate of recovery pared with the treated oils, the several varnishes 5 t the original condition. The hot water test was then being subjected to drying and water tests Carried out in a similar manner, exc p that e with results indicated in Table No. IB herebep n ls We immer ed in boili Wa r f r 5 low. The varnishes were prepared with ester minutes; the milkiness nd rate o r y a n gum, each being of 25 gallon length, and each being varnish was cooked at 3 09 C to a iscosity f 10 The columns under the Cold water and Hot about C to D, at 50% solids when thinned with er h d ngs indicate the following: mmeral e e rttme requlred to Con=arbitrary scale of condition of film when reach thls vlseeslty 1s mdlea'ted m the table first removed after the test, No. 1 indicating the best condition, explanatlon of the deslgee'tiens under the Rec=arbitrary scale representing rate of recovdrymg other test e 1S glven after the ery to original condition after withdrawing table, but it is here pointed out that the followfrom the test, No. 1 indicating the best rate mg as well as other tables, appearing In t D ON==arbitrary scale of the condition ofthe film em speclfiea'twn Include (In addition to after standing overnight (following immersion bered examples) letteredmxamples which repreperiod) No. 1 indicating the best condition sent blank or control experiments, 1. e., an experiment carried out with the same on under The alkali resistance test was carried out with exactly the Same treatment conditions as the somewhat heavier films than for the drying test, numbered examples, except that no treating agent and cold Water i Water teststhis was used. It may also be mentioned that statepose films of 0003 thlckness were apphed to test merits regarding comparisons of properties, such panels which e eheeimmersed in a aqueous as drying characteristics, are always related to sedlun? hydreeflde selutlon' The eondltwn afterr films formed with varnishes incorporating the hours lmmerslen, was Observed e reeerded e same fatty oil treated under the same conditions also the co'ndltloh after ve night immersion. (both prior to and during the formation of the The results of these Observatlons are varnish itself) but without the presence of the Gated, mfithe eorrespondmg columns wider the modifying or treating agent, heading Alkali. The key to the letters in these In the table just below the example numbers columnsls as fellows: correspond to those in Table No. I-A, the letter H=hazy v following the example number indicating the Sl.m=slightly milky varnish prepared with the treated oil. M=milky Table No. IB VARNISHES PREPARED WITH TREATED OILS or TABLE No. IA

Minutes Drying Cold water Hot water Alkali EL No cooking Visat 300 cosity C. Set DF TF ON 48 Con Rec ON 0011 Bee ON 7hrs. ON

164 A 1 B A 3 2 2 5 2 2 207 o 1 D A 2 1 1 5 2 1 203 o 4 B A 2 1 1 5 1 1 5 O M O B 4' 2 1 5 2 1 161 D 4 o A 2 1 1 5 1 1 190 o 1 2 2 D- A 1 1 1 5 3 2 Set=time in hours to initially set.

DF=time in hours for the film to become dustfree.

'IF=time in hours for the film to become tackfree.

ON=condition of film after "overnight drying,

the letters representing an arbitrary scale to indicate the relationship between the several ex amples, and also their relation to the item just below (the letter A indicates the driest film and succeeding letters progressively decrease in hardness). 48=condition of film after drying for 48 hours.

Where appreciable dissolution of the film took place, that fact is noted in the corresponding columns by figures, representing the approximate percentage of the film remaining. For instance, M40 indicates that the film was milk and that 40% of the immersed part of the film remained on the panel, 60% being destroyed.

With the foregoing explanatory comments in mind, it will be seen from Table No. IB that notwithstanding the appreciable loss in treating agent during the initial treatment of the oi1 (see Table I--A),'the varnish films displayed considerable improvement in a number of respects as compared with a film made from a varnish incorporating the same oil in untreated condition (compare Example Av with the others). The alkali resistance and drying characteristics both display considerable improvement.

COMPARATIVE EXAMPLES 6 T0 9 In this series of examples alkali refined linseed oil was also used and was treated with 2% resorcinol, as in the first series. In each case a batch of 400 gms. of oil was placed in a one liter Erlenmeyer flask equipped with a reflux condenser, so as to provide a condition of pre-condensatien and thereby reduce loss of the resorcinol. For the reflux condenser, a straight air condenser was used, since the relatively high boiling point of resorcinol does not necessitate water cooling. In all experiments of this series the refluxing time was two hours. The temperatures tried difiered as between different examples. the results being indicated in the Table IIA herebelow,

Table No. I,IA

LINSEED OIL WITH RESORCINOL ALKALI REFINED UNDER REFLUX Vis- Extent .of

Temperature cosity sublimation 6. W... l50 C A Very little. 7.. 200C B Do. 8. 250 C U DO. 9 300 C 'I Do.

B (The same 011 without heating A and not refluxed.)

As in Examples 1 to .5, the treated oils .of Examples 6 to 9 were also used in preparing ester gum varnishes of gallon length, the formulation being the same as described above. These varnishes were then tested and the results are indicated in Table IIB just below, incorporating columns and distinctions corresponding to those described above.

COMPARATIVE ExAMPLEs 10 To 12 V blanket of CO2 was maintained at the surface 1 about Z4 to Z6 viscosity. Results of this series Table No. II-B of the oil and all of the oils were heated under reflux preliminarily for two hours at 200 C. and thereafter for an additional period at 300 C. for a time sufficient to increase the body to from of examples are indicatedin Table No. III-A.

Table No. III-A ALKALI REFINED LINSEED OIL WITH VARYIN G PERCENTAGE OF RESORCINOL Ex. No. Percentage Time at 300 C. Viscosity 0.5% .8 hrs, 10 mins Z5 2.0%., 8 hrs, 40 mins Z4 4.0% 7 hrs Z6 No agent 8,hrs., 20 mins Z5 From the above it will be seen that lower than VARNIS'HES PREPARED W ITH TREATED OILS OF TABLE NO. II-A Minutes Drying Cold water Hot water Alkali Ex N0 cooking V s- V v V at 300 cosity a C. V Set DF Tl? ON 48 0011 Bee ON Con Rec ON ,7 hrs. ON

189 Cv V), B A 3 1 l 5 1 l 210 C 1 C A 2 2 2 5 2 1 210 D B A 2 1 1 6 '1 1 105 D i. A D A l 1 l 5 l l 190 C l 2 I 2 D- A l 1 l 5 3 2 The faster bodying of the varnish of Example 911 may be partly'explained by the fact that the oil here employed (see Table II-A) had a much higher viscosity than the ther oils, indicating that at least a portion of the bodying took place during refluxing.

The foregoing table shows that cold and, boiling water resistance and also the alkali resistance were quite satisfactory and further that about 4% of resorcinol does not materially accelerate the rate of bodying.

To demonstrate drying and other characteristics of these treated oils, 25 gallon length ester gum varnishes were again prepared and cooked in a manner similar to those described above, except that the viscosity attained was about from C to E. The properties of these varnishes are indicated in Table III-B just below.

Table No. IIIB VARNISHES PREPARED WITH TREATED OILS or TABLE NO. IIL-A Minutes Drying Cold water Hot water Alkali EX N0 cooking V sat 300 cosity C. Set DF TF ON 48 Con Rec ON Con Rec ON 7 hrs ON C 1% 3 4 B A 2 2 1 6 5 5 M Gone. 116 C 1% 2 3 B A- 2 2 l 5 2 .2 S1. m Do. 90 D 1% 3 8 D A 1 l 1 6 5 5 H Do. E V2 1% 2 'D A 2 2 1 5 1 1 1-1 Do.

tion by refluxing between about C, and 250 C. gives the most advantageous results.

From the foregoing, it may be noted that while the resorcinol, When used in low percentages, does not appear to appreciably accelerate the rate of bodying of the oils, nevertheless, considerable improvement With'respect to rate of bodying is observable in preparing or cooking the varnishesfrom the pro-treated oils.

The varnishes made with oil containing 0.5% resorcinol (1011i and 2% resorcinol (1112) both showed up quite well in various of the drying and other tests. The varnish containing 2% resorcinol (1112) seems to yield the best results,

EXAMPLE 13 lowing percentages of resorcinol,

Example N0. Resorcinol Per cent 13a 1.0 0.5 0.2 0.1 138 0.

Heavy bodied oils were prepared of each of the diluted oils, and also of a portion of the 2% batchv initially prepared, by bodying them to Z-4 to Z-6 viscosity.

Varnishes were then prepared with each of the '1' above heavy bodied oils. These varnishes were prepared with ester gum iii twenty-five gallon length, and each varnish was cooked to ard viscosity. v I i i All of the varnishes were tested in accordance with the methods set out above, and in general all batches showed improvements in at least certain respects, as compared with a similar varnish made in essentially the same way but not containing resorcinol-treated oil. Some of the specific results were'as follows: I

In cold water resistance, the 2% resorcinol containing oil yielded the best results, although these results were approached by the varnish prepared with the 0.05% resorcinol containing oil., In the boiling water test, the results were similar to those in cold water. v a

In alkali resistance, the several batches may a stand- 10 ing the oil under pre-condensation or refluxing at a temperature of about 150 C. and for a time of abouttwo hours. That these conditions constitute about the most favorable balance, when considering the various diiferent characteristics and properties, is further evidenced by the results of another comparative series of examples given justbelow.

COMPARATIVE EXAMPLES 14 '10 17 p In this series of examples alkali refined linseedoilwas'again used and in each example 2% of resorcinoiwas employed as'the treating agent. The batch of each example was preliminarily heated under refluxfor two hours, the refluxing temperature being different as be t'we'en the several examples. Thereafter, the treated oil "of each batch was heat bodied at 300 C. for a time of about'3 hours. (The viscosities obtained in the given time are indicated in Table IV-A just below. V J H L Table NO. IV-A NG 0F BESORCINOL TREATED 'ALKALI HEAT BODYI I 'REFINED LINSEED OIL Reflux temperature The foregoing indicates that refluxing at about viscosity (Z-G) secured with.the:oil refluxed at 300 C. (Exarr'1pl'e"1'7)w is apparently due to the. factthatat least a portion: of the heat bodying took place duringcthe refluxing itself.; Ester gum varnishes oi 'tWenty-five' gallon lengthwere prepared from 'thelfforegoing bodied oils ',"the preparation being according to the form- 1115. and process already described above in connection with otheriexamples; ,The'drying and other properties of the varnishes thus prepared are indicated in the following table.

Minutes Drying Goldwater Hot water Alkali EX No cooking Visat 300 cosity j C. Set DF TF ON 48, 0011v Rec ON 0on- Rec. ON 7hrs 0N 14v O x 1 B A 1 1 1 5 g 11 1 H M. 15v 90 D M; A 1 D A 1 .2 1 5 1 l H .M-70. 161; 90 D 56 M 1 C A 2 Y 1 1 5 l 1 S1. m Gone. 1711 55 O 36 1 -B ,A 2 l v 1 5- l 1 M M-20.

be graded in the following order of percentage of resorcinol contained in the oil used, the first figure showing the best results and the others gradually decreasing in alkali resistance: .1%, 0.5%, 0.05%, 0.2%, 2%, and 0.1%.

From this series'of tests it will be seen that certain of the properties of the treated oils and varnishes made therefrom are not necessarily proportional to the quantity of resorcinol present. Therefore, for individual uses and applications, the concentration most favorable to that purpose should be selected.

Various of the foregoing comparativeexamples indicate that for an all roundtypeof prod-- uct, an efiective balance of desirable properties The foregoing table lshows highly desirable properties, especially with the example. (Example 14) employing; 2%,re sorcinol,';refluxed for two hours at 150'C. A" varnish made with this particular oil shows excellent cold water re-- sistance,- good hot water resistance andv good alkali resistance. It is tack-free in one hour and really hard in forty-eight hours.

As hereinbefqre mentioned, for certain purposes it may betdesirable to' treat'the oil not only with resorcinol' orother polyhydroxy ben-. zenes, but also withsome other agent'or agents; h may ea ra iegeoq whe ei d to im v .e a nsnesif q; pro e i s fo ins nc alkali resistance; drying, speed of varnish bodyis secured by the employment of resorcino l ining, etc. Examples 0 ar s y nha w'r;

f such composite treatment sulpho-salicylic acid A-batch of 4,000gms. of alkali refined linseed oil was heated with 0.5% sulpho-salicylic acid at 100 C., until the reagent dissolved. Theheating was carried out in a three gallon openrkettle with All three of'the above oils were then: heat bodied to aviscosity of from 2-4 toZ- fi and.25 gallon long ester gum varninshes were prepared with the bodied oils in the manner described above,

the several varnishesbeing'tested in the manner described above, and giving the-following resultsfi shoe-33'? V dtherbeing .alkali.refined linseed oil contain ng 7 r 2 resorcinol alone (without thesulpho salicylic 12 was prepared in the manner already described, yielding in the short time of 60 minutes a viscosity of G at 50% solids (cut with mineral spirits).

Although the alkali resistance of the varnish was somewhat reduced as compared with a varnish containing an oil made with resorcinol alone,

bythe conjoint use of maleic anhydride-the bodying velocity was greatly increased, and in addition, the drying time, cold water and boiling'water ,resistancewereah very satisfactory.

treated linseed oil was employed as a starting material, the oilcontaining beta-methyl-anthraquinone'as an agent for acceleratingheat bodying. This oil had a viscosity about the same as alkali refined or raw linseed oil.

' Seventy pounds of the treated oil were heated in a 15 gallon kettle with 2% resorcinol under reflux for 2 hours at 15010. A 5,000 gm. batch of the resorcinol treated oil was then bodied at Table No.- V-' I 7 Minutes I O V 713%. ss eg g g Xiiifitt Dwmg wit; watt Alkali 18.-. 2% resorcinol-F595 sulpho-sal V .172 E Fain-.. Very good v ery gooi (iced after 7 hrs.; gone overnight Dz)"; Oil Without any agent- 135 E Fair-k--. G00d Gopd GoneZhrs. I V Ev' 2% resorcino1 ,lld 0 Good do Fair Gone 3% hrs,

Although; the above table indicates that the sulpho-salicylic acid slightly decreases the bodying speed and the drying velocity of the resorcinol treated oil, it is noted that the presence orthe contributesto very good hot and cold water resistance and. also greatly; in

creases the alkali resistance. (It may be mentioned that for the alkali tests in Table V films of only .00.15 inch thickness were. employed, which is in contrast tothe heavier films (.0030) used in other examples.)

EX MPLE 19 i gm. of alkali refined linseedoil was refluxed with 2% resorcinol at 150 C. Thereafter, 0.5% of naphthionic acid was added to the cil'and the temperature raised to 300- -C.

' for 5 /2 hours, under a blanket of co This Se- C red a viscosity of Z'5 and from this "treated oil a gallon long'ester gum varnish was prepared in accordance with the above description;

yielding after a 2 /2- hour cookingat 300 C., a viscosity of'D,v at solids. The resultingvarnish, had substantially improved alkali resistance compared tovthat of a similar varnishmade with a similar oil containing resorcinol alone.' The drysistance Were somewhat better than that of the varnish made with an oil treated only with.

resorcinol.

EXAMPLE 20 2% resorcinol, by refluxing'the reaction mixture for two hours at 150 C. After the precondensaing velocity, cold water. and boiling water re- I tion period-(therefiux condenser was eliminated and thetemperature of the' oil raised to 295 C.

hours and 10 minutes yielding a viscosity 4 1 H re again a 25 gallon long ester giimwajr nish 300". Qior two hours and twenty minutes, under a blanket of CO2, yielding a-viscosity of X. t

The ioregoing treated and heat bodied oil was then employed in the preparation of 25 gallon ing times and viscosities' are indicated in the z iollowing tablep U 'Table VI EXLNO. Resin 7 Viscosity 7 21a Ester gum 315 K 2lb.- Para11o1l750 35 C '2le. Amberol 801... 65 I The foregoing varnishes were subjected to tests of the types described above, the results indicating that the cold Water'and boiling water'resi'slh ancewere somewhat improved-as compared to a similar varnish made with oil containing betamethyl-anthraquinone, but not containing resorcinol. The drying'properties and alkali resist-' fance were'both substantially improved as com- ,pared with the varnishes not containing resorc-inol. r r a (or varnish bases) prepared withthe oil treated only with beta methyl anthraquinone, and with The most striking improvement, however, is V the increasein the rate of bcdyin'g, as compared said all further treated with resorcinol, it may be noted that, if properly pre-bodied to a viscous oil, it will be found that in the cooking of varnishes (or varnish bases) the oil (without resorcinol) will further body fairly rapidly. The addition of resorcinol to the treated oil (containing betamethyl-anthraquinone) imparts a slight but still further increase in bodying velocity. Such acceleration of bodying is noticeable, for instance with varnishes (or varnish bases) prepared withester gum. However, the more important improvement imparted to this treated oil by the further additionof resorcinol is the improvement in drying and also some of the other properties, for instance alkali resistance.

It, therefore, appears that such conjoint treatment with resorcinol and certain other agents not only achieves the advantages of resorcinol, but at the. same time secures other improvements in properties, notably the velocity of bodying. Particularly .useful products may be secured by conjoint treatment with a polyhydroxy benzene and with other modifying agents such as organic acids (polycarboxylic acids), condensed rin compounds and organic sulfonic acids, examplesof whichare given in my Patents 2,298,- 914, 2,298,915, and 2,298,917.

In four examples referred to below, oils were treated in accordance with this invention, with somewhat diiferent procedures in each case. Thereafter, comparative varnish formula were made employing these oils. The treatment of the oils is first referred to just below under individual example numbers, following which the varnish preparation and results are described.

EXAMPLE 22 A batch of 150 gms. of linseed oil was heated in a 500 cc. Erlenmeyer flask with 7 gms. of resorcinol for 5 hours at a temperature between about 200, and 220 0., the batch being kept under a vacuum of 26 to29 inches. The temperature was just below the boiling point and the treated oil was-a somewhat bodied clear mobile oil. Although no extensive changes Were visible in the oil itself, improved properties were secured in varnishes, as brought out below.

' EXAMPLE 23 nan/rm.- 24

A batch of 150 gms. of linseed oil was heated with gins. of; resorcinol in a Pyrex flask under air reflux. Solution of the resorcinol had been attained when the temperature rose to 220 C.

yielding an amber colored oil. At about 306 C.

the batch was simmering gently, but developed some vigorous bumping, so that for a-short time the refluxing was replaced by a distillation connection; Very little of the material distilled. The refluxing was continued at 300 C. until, after 1 /2 hours, the reflux condenser was taken ofi, heating being continued under open atmospheric conditions at 280 C. to 300 C. for 3 hours. The total time between 280 and 306 C. was 6 1,4. hours, and the product at this stagewas a fairly thin clear oil. The treated oil was thereafter further heated by continuing heating at 290,to 310 C. for two hours, after which heating the oil was consid After cooling overnight, the

EXAMPL 25 v A; batch of linseed oil was heated in a manner similar to that described above in connection with Example 23, the treating agent, however, being Pyrogallol (1, 2, 3, trihydroxy benzene) instead of-resorcinol. The oil was heated between and 200 C. for 3 hours and then between 280and 300 C. for 4 hours, and finally kept at 320 C.-for 50 minutes.

300 0., but thereafter the bodying was rapid and the finalproduct, when cold, was a gelatinous solid.

CQMPARATIVE EXAMPLES 22v 'ro 25v The final oil products of Examples 22 to 25 were employed in the preparation of batches of varnishes made of 25 gallon length with lime hardened rosin, the varnishes being diluted to 50% solids with mineral spirits. These varnishes were tested for drying and other properties and in each case, the varnish was tested in four different forms as follows:

a. Varnish without drier.

b. Varnish plus cobalt drier (0.03 cobalt metalon the basis of oil content). I

c. Zinc oxide paint made with the varnish without drier (pigment to vehicle solids ratio=1 to 1 by Weight).

d. Zinc-oxide paint as per 0, with drier as per b.

treated oils was also improved as compared with the blanks, the several examples showing up the following order, the best drying being placed at the top of the list and being far superior to the I following:

Varnish made with oil of Example 24, containing 10% resorcinol.

Varnish made with oil of Example za cn tai ing 5% resorcinol.

Varnish made'with oil of Example 25, containing 5% Pyrogallol.

Varnish made with oil of Example 22, containing 5% resorcinol.

In the varnishes containing cobalt drier, the Y 7 No appreciable bodying took place until the temperature exceeded about In the ,paints. not containing cobaltdrier. the results were similar to the varnishes, the four ex-- paints was that notwithstanding the use of lime hardened rosin asthe resin ingredient; very good water resistance was secured, especially-in the paints made with the oils of Examples25, 23 and 24;,and with the clear varnish made with the treated oil of Example 25.

I claim: c 7 r 1.. A process for treating up to 30% of resorcinol as the sole active treating agent, and heating the mixture at a temperature V between the dissolution point of the resorcinol and about 310 C. for at least 30 minutes.

2. A process in accordance with claim 1 in which the heating of the oil containing resorcinol is effected in two stages,the first of which is con.- tinuedfor at least 30 minutes at a temperature not exceeding about'200 Cr and the second of which is continued for at least 30 minutes at a temperature above about 200 C. Y

3. A process in accordance with'claim 1 in which the heating of the oil containing resorcinol is efiectedin two stages, the first of which is -continued for at least 30 minutes at a temperature not exceeding about 200 C; and the second of which is continued for at least 30 minutes at a temperature above about 200 C'., said first stage being carried out under refluxing conditions.

l. A process for treating'fatty oils having dry- 7 ing properties, to improve their characteristicsas components of surface coating compositions, which process comprises incorporating in the oil up to 10% of resorcinol as the sole active treating agent, and heating the'mixture under refluxing conditionsat a temperature between about 75 C. and about 250 C. for at least 3.0

minutes.

5. A process in accordance with. claim 4.- and further comprising additionally heatingthe refluxed mixture ata temperature between about 250 C. and about 310 C. for at least 30 minutes.

6. A process for treating fatty oils having dry ing properties, to improve their film-forming.

. characteristics when used as components oi'surface coating materials, which process comprises incorporating in the oil up to 30% of a polyhydroxy benzene as the sole active treating agent, and heating the mixture at'a temperature between about 75 C. and about 350iC. but not above the boiling r decomposition point of the oil, whichever is lower, for at least 30 minutes.

fatty oils having dry: ing properties to improve their characteristics, as components of surface coating compositions, which process comprises incorporating in the oil face coating materials-which process comprises incorporating in the oil up to 30% of a polyhydroxy benzene as the sole active treating agent, and heating the mixture at a temperature between aboutv C. and about310 C". for at least 30 minutes. r

8. A process in accordance with claim 7 in which said polyhydroxy benzene is a dihydroxy benzene.

.9. A processin accordance with claim '7 in which said polyhydroxybenzene is a trihydroxy benzene.

I 10. A process in accordance with claim 7' in.

which said polyhydroxy benzene is pyrogallol.

11. A process for treating fatty oils having drying properties, to improve their film-forming characteristics when usedas varnish base materials, which process comprises incorporating in the oil up to 10% of resorcinol as the sole active treating agent, and. heating the mixture at atemperature between about 75 C. and about 310 C. for at least 30 minutes. i

12. A process in accordance withclaim 11 in which at least a portion of the heating is effected under refluxing conditions.

13. A process in accordance with claim 11 in which an initial ortion of the heating is effected at a relatively low temperature under refluxing conditions, and in which a succeeding portion of the heating is eifected at a relatively higher temperature sufiicient to effect heatbodying.

14. A process in accordance with claim 11 in which the fatty oil is'sele'cted from the class comprising drying fatty oils and semi-drying fatty 'oils.

v 15. A process in accordance with claim 11 in which the fatty oil is linseed oil. 1

16. A process in accordance with claim 11 in which the fatty oil is 'soya bean oil. 7

17. A process in accordance'with claim 11 in which the fatty oil is a pentaerythritol ester con-i taining linseed'oil fatty'acids.

g 18. A varnish comprising a ing from about .05% to about30% of resorcinol as the sole added treating agent, a varnish resin and a volatile solvent. 7 I

19. A varnish comprising a fatty oil-containing from about .05% to about 30% of pyrogallol' as the sole added'treating agent, a varnish resin.

and a volatile solvent. r s

-20. A process for treating fatty oils having drying properties to improve their film-forming characteristics when used ascomponents of surface coating compositions which process come prises incorporating in the fatty oil up to 5% of resorcinol asxthe sole active treating agent, precondensing the resorcinol with the oil at a temperatu're below about 250 C. and thereafter heat bodyingthe oil by heating the mixtureto a heat bodying temperature above about 250 C.

21..'A process in accordance with claim 4, in which. the quantity of resorcinol used is between V V /2% and 2% of the weight of the oil,

'7. A process for'treating'fattybils having drying properties, to improve theirufilm-formingf I characteristics when used as components of sur-'- v22.' A process inaccordance with claim '11; in whichiat least a portion of the heating is effected under refluxing conditions and the temperature of the refluxing'being at; least C. and not more than 200C. and therefiuxing time. being at 1east30 minutesj fatty oil contain I emme. 

